4.7 Article

Detoxification of Ciprofloxacin in an Anaerobic Bioprocess Supplemented with Magnetic Carbon Nanotubes: Contribution of Adsorption and Biodegradation Mechanisms

Journal

Publisher

MDPI
DOI: 10.3390/ijms22062932

Keywords

anaerobic reduction; adsorption; ciprofloxacin; magnetic carbon nanotubes; redox mediators; toxicity

Funding

  1. Portuguese Foundation for Science and Technology (FCT) [UIDB/04469/2020]
  2. European Regional Development Fund under the scope of Norte2020-Programa Operacional Regional do Norte [NORTE-01-0145-FEDER-000004]
  3. FCT [CEECINST/00049/2018, SFRH/BD/131905/2017, SFRH/BD/132003/2017]
  4. Associate Laboratory LSRELCM - national funds through FCT/MCTES (PIDDAC) [UIDB/50020/2020]
  5. Fundação para a Ciência e a Tecnologia [SFRH/BD/131905/2017, SFRH/BD/132003/2017] Funding Source: FCT

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The study investigates the potential of carbon nanomaterials (CNM) as redox mediators in anaerobic bioreactors for the removal of ciprofloxacin (CIP). Results show that the presence of CNM can accelerate CIP removal and reduce its toxicity after biological treatment.
In anaerobic bioreactors, the electrons produced during the oxidation of organic matter can potentially be used for the biological reduction of pharmaceuticals in wastewaters. Common electron transfer limitations benefit from the acceleration of reactions through utilization of redox mediators (RM). This work explores the potential of carbon nanomaterials (CNM) as RM on the anaerobic removal of ciprofloxacin (CIP). Pristine and tailored carbon nanotubes (CNT) were first tested for chemical reduction of CIP, and pristine CNT was found as the best material, so it was further utilized in biological anaerobic assays with anaerobic granular sludge (GS). In addition, magnetic CNT were prepared and also tested in biological assays, as they are easier to be recovered and reused. In biological tests with CNM, approximately 99% CIP removal was achieved, and the reaction rates increased approximate to 1.5-fold relatively to the control without CNM. In these experiments, CIP adsorption onto GS and CNM was above 90%. Despite, after applying three successive cycles of CIP addition, the catalytic properties of magnetic CNT were maintained while adsorption decreased to 29 +/- 3.2%, as the result of CNM overload by CIP. The results suggest the combined occurrence of different mechanisms for CIP removal: adsorption on GS and/or CNM, and biological reduction or oxidation, which can be accelerated by the presence of CNM. After biological treatment with CNM, toxicity towards Vibrio fischeri was evaluated, resulting in approximate to 46% detoxification of CIP solution, showing the advantages of combining biological treatment with CNM for CIP removal.

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